[go: up one dir, main page]

EP2323960B1 - Verfahren zur herstellung eines silicium/kohlenstoff-verbundwerkstoffs - Google Patents

Verfahren zur herstellung eines silicium/kohlenstoff-verbundwerkstoffs Download PDF

Info

Publication number
EP2323960B1
EP2323960B1 EP09782886.7A EP09782886A EP2323960B1 EP 2323960 B1 EP2323960 B1 EP 2323960B1 EP 09782886 A EP09782886 A EP 09782886A EP 2323960 B1 EP2323960 B1 EP 2323960B1
Authority
EP
European Patent Office
Prior art keywords
process according
silicon
polymer
silicon particles
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP09782886.7A
Other languages
English (en)
French (fr)
Other versions
EP2323960A2 (de
Inventor
Mélanie ALIAS
Frédéric Le Cras
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Publication of EP2323960A2 publication Critical patent/EP2323960A2/de
Application granted granted Critical
Publication of EP2323960B1 publication Critical patent/EP2323960B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62828—Non-oxide ceramics
    • C04B35/62839—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6267—Pyrolysis, carbonisation or auto-combustion reactions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for preparing a silicon / carbon composite material.
  • the silicon / carbon composite material prepared by the process according to the invention can be used as an electrochemically active electrode material, in particular a negative electrode, in non-aqueous organic electrolyte electrochemical systems, such as Rechargeable electrochemical accumulators with organic electrolyte, especially in lithium batteries and even more specifically in lithium ion batteries.
  • electrochemically active electrode material in particular a negative electrode
  • non-aqueous organic electrolyte electrochemical systems such as Rechargeable electrochemical accumulators with organic electrolyte, especially in lithium batteries and even more specifically in lithium ion batteries.
  • the technical field of the invention can be defined in a general way as that of the electrodes used in electrochemical systems with non-aqueous electrolyte, organic and more particularly as that of rechargeable accumulators with organic electrolyte such as accumulators, lithium batteries and more particularly the accumulators, batteries with lithium ions.
  • Lithium technology offers the best features compared to other technologies present.
  • the lithium element is the lightest and most reductive metal and electrochemical systems using lithium technology can reach voltages of 4V against 1.5 V for other systems.
  • Lithium ion batteries have a specific energy density of 200 Wh / kg against 100 Wh / kg for NiMH technology, 30 Wh / kg for lead, and 50 Wh / kg for NiCd.
  • the current materials and in particular the electrode active materials reach their limits in terms of performance.
  • active electrode materials consist of an electrochemically active material which constitutes a host structure in which the cations, for example lithium cations, are inserted and disintegrated during cycling.
  • the most commonly used negative electrode active material in lithium ion batteries is graphite carbon, but has a low reversible capacitance and exhibits an irreversible loss of capacitance "ICL".
  • silicon represents a desirable alternative to carbon. Nevertheless, this material has a major disadvantage preventing its use. Indeed, the volume expansion of the silicon particles of nearly 300% during charging (Li-ion system) leads to the cracking of the particles and the separation of the latter from the current collector.
  • Si / C composites have a better cyclability than pure silicon but show a drop in capacity after a number of charge-discharge cycles. This can be explained by the microstructural change of the silicon during the cycling, because the silicon particles swell up to burst and unhook from the electrode. The contact is not sufficiently intimate between the carbon and the silicon so that the carbon compensates the voluminal changes of the silicon.
  • the document by ZHANG et al. [1] describes the preparation of composite materials based on disordered carbon and nanoscale silicon by mechanical grinding and then pyrolysis. More precisely quantities Silicon powder and poly (vinyl chloride) (PVC) or poly (paraphenylene) (PPP) are milled mechanically in a ball mill for 24 hours to give Si-polymer composites in which the Si particles are coated with the polymer.
  • PVC polyvinyl chloride
  • PPP poly (paraphenylene)
  • Si-polymer composites are then heated at 650 ° C., 800 ° C. and 900 ° C. for two hours under an argon atmosphere, whereby the final composite material based on nanometric silicon and disordered carbon is obtained.
  • Composite anodes for lithium ion accumulators are then prepared by applying a suspension containing 80% of the silicon / carbon composite material, 10% of carbon black as an electronically conductive additive, and 10% of polyvinylidene fluoride ( (as a PVDF binder) in 1-methyl-2-pyrrolidone (NMP) on both sides of a copper cloth.
  • the Si / C composite material prepared in this document [1] has a very irregular morphology and an uneven particle size because of this grinding.
  • the LIU et al. [2] discloses a method for preparing a disordered silicon / carbon composite material for lithium ion accumulator anode, wherein PVC and silicon particles smaller than 1 micron in size are homogeneously mixed, then the mixture is pyrolyzed a first time at 900 ° C in an argon atmosphere and cooled. The product thus obtained is then subjected to high-energy mechanical grinding ("HEMM") in a closed chamber under argon. The samples thus obtained are again mixed with PVC and the mixture is pyrolyzed a second time under the same conditions as during the first pyrolysis, and the samples thus pyrolyzed are crushed and sieved.
  • HEMM high-energy mechanical grinding
  • the material thus prepared shows a stable capacity at 900 mAh / g after 40 cycles and a faradic efficiency in the first cycle of 82%.
  • the resin is first dissolved in ethanol, then nanoscale silicon powder and fine graphite powder are added to the PF resin solution to thereby obtain a suspension containing graphite particles and of silicon.
  • This suspension is then subjected to a drying-spraying operation at the end of which spherical particles or spheroids of Si / precursor PF are obtained which are heated at 1000 ° C. for 2 hours, whereby a Si / C composite is obtained.
  • This Si / C composite can then be dispersed in a PF solution and then undergo the same steps of spray-drying and pyrolysis, whereby a carbon-coated Si / C composite is obtained.
  • the capacity of the composites of this document [3] increases during the first cycles up to 635 mAh / g to reach 500 mAh / g after 40 cycles.
  • the theoretical capacity of the composites of document [3] should be 1363 mAh / g, but we have seen that the practical capacity is 635 mAh / g, only 50% of the theoretical capacity.
  • a micrometric silicon powder is mixed homogeneously using a ball mill with a given amount of precursor (PVdF, sucrose, PVC, PE, PEO, CPE). The mixture is then pyrolyzed at 900 ° C. in an Argon / hydrogen atmosphere for 1 hour. The samples are cooled and further ground.
  • precursor PVdF, sucrose, PVC, PE, PEO, CPE
  • nanometric silica 60 nm is added to an organic precursor solution, for example a solution of PVDF in THF, and homogeneously mixed under the action of ultrasound. The solvent is evaporated with stirring to give a solid mixture which is pyrolyzed at 900 ° C in an Argon / hydrogen atmosphere for 1 hour. The samples are cooled and further ground.
  • organic precursor solution for example a solution of PVDF in THF
  • the object of the present invention is to provide a method for preparing a carbon-carbon composite material that meets the needs mentioned above, among others.
  • the object of the present invention is still to provide a process for preparing a silicon / carbon composite material which does not have the disadvantages, defects, limitations and disadvantages of the processes of the prior art, and which solves the problems of the methods of the prior art.
  • the method according to the invention comprises a specific sequence of specific steps which has never been described in the prior art.
  • the process according to the invention is fundamentally different from the processes of the prior art, and in particular processes of the prior art using an atomization-drying technique in that the polymer used is a polymer without a d oxygen, oxygen-free, does not contain oxygen.
  • the performance of a lithium ion accumulator comprising as an electrode active material, and in particular a negative electrode, the composite material prepared by the process according to the invention are also greatly improved with respect to an accumulator of which the electrode active material, and in particular the negative electrode, consists of an Si / C composite material prepared by a process that does not involve atomization-drying such as grinding or chemical vapor deposition (CVD).
  • the method according to the invention has on the one hand all the advantages inherent in the atomization-drying process in that it makes it possible to control the particle size and the morphology of the polymer / Si composite before the pyrolysis. which then ensures a strong contact at the interface between the silicon and the carbon after pyrolysis, but it does not not, on the other hand, the disadvantages associated with the use of a polymer comprising oxygen.
  • the method according to the invention does not have the disadvantages of the processes of the prior art and provides a solution to the processes of the prior art.
  • the polymer may be chosen from polystyrene (PS), polyvinyl chloride (PVC), polyethylene, polyacrylonitrile (PAN) and polyparaphenylene (PPP).
  • PS polystyrene
  • PVC polyvinyl chloride
  • PAN polyacrylonitrile
  • PPP polyparaphenylene
  • the solvent may be chosen from halogenated alkanes such as dichloromethane; ketones such as acetone and 2-butanone; tetrahydrofuran (THF); N-methylpyrrolidone (NMP); acetonitrile; dimethylformamide (DMF); dimethylsulfoxide (DMSO); and their mixtures.
  • halogenated alkanes such as dichloromethane
  • ketones such as acetone and 2-butanone
  • N-methylpyrrolidone (NMP) tonitrile
  • DMF dimethylformamide
  • DMSO dimethylsulfoxide
  • the polymer may be polystyrene, and the solvent may be 2-butanone.
  • the concentration of the polymer in the solution may be from 10 g / liter of solvent to 200 g / liter of solvent.
  • the silicon particles may be micrometric particles, that is to say particles whose size defined by their largest dimension (ie for example the diameter in the case of spherical particles) is from 1 to 200 microns, preferably from 1 to 45 micrometers.
  • the silicon particles can be nanometric particles, that is to say particles whose size defined by their greater dimension (that is to say for example the diameter in the case of spherical particles) is 5 to 1000 nanometers, preferably 5 to 100 nanometers.
  • the nanoscale silicon particles may in particular be silicon particles synthesized by reduction of SiCl 4 under a controlled atmosphere, that is to say preferably under argon.
  • step a) is then carried out under a controlled atmosphere, preferably under argon.
  • the concentration of the silicon particles in the dispersion can be from 0.1 to 50 g / l.
  • the silicon particles coated with the polymer are spherical in nature with a diameter for example of 1 micrometer to 20 microns.
  • it is generally a spherical or spheroidal composite material containing silicon particles trapped in a polymer matrix.
  • step b) the dispersion is sprayed into droplets by a nozzle raised to a temperature of 20 ° C to 220 ° C, preferably 60 ° C to 110 ° C.
  • step c) is carried out at a temperature of 600 ° C. to 1100 ° C., preferably 800 ° C. to 900 ° C.
  • step c) can be carried out under a controlled atmosphere such as an argon or argon and hydrogen atmosphere.
  • the carbon-coated silicon particles form clusters and have a nanometric dimension.
  • the composite material obtained by the process according to the invention finds particular application as electrochemically active electrode material in any electrochemical system.
  • this electrode is a negative electrode.
  • the electrochemical system can be a rechargeable electrochemical accumulator, non-aqueous electrolyte which therefore comprises the silicon / carbon composite material prepared by the process according to the invention as an electrochemically active electrode material, preferably a negative electrode.
  • a negative electrode further comprises a binder, optionally one or more electronic conductive additives, and a current collector.
  • the composite material prepared by the process according to the invention is the positive or negative electrode active material of a lithium ion rechargeable battery, but it is quite obvious that the following description can easily be extended and adapted, if necessary, to any application and method of implementation of the composite material prepared by the process according to the invention.
  • silicon particles are mixed with a solution in a solvent of a polymer containing an oxygen atom, whereby a dispersion of silicon particles in the polymer solution is obtained.
  • the polymer is a polymer without oxygen atom, containing no oxygen, free of oxygen atoms.
  • This polymer may be chosen in particular from polystyrene (PS), polyvinyl chloride (PVC), polyethylene, polyacrylonitrile (PAN) and polyparaphenylene (PPP).
  • PS polystyrene
  • PVC polyvinyl chloride
  • PAN polyacrylonitrile
  • PPP polyparaphenylene
  • the preferred polymer is polystyrene (PS) because of its lack of toxicity, because it is inexpensive, and because it does not release chlorine.
  • PS polystyrene
  • the solvent of the polymer solution may be selected from a wide variety of solvents.
  • this solvent can be chosen from halogenated alkanes such as dichloromethane; ketones such as acetone and 2-butanone; tetrahydrofuran (THF); N-methylpyrrolidone (NMP); acetonitrile; dimethylformamide (DMF); dimethylsulfoxide (DMSO); and their mixtures.
  • Table 1 indicates the solvents in which polyvinyl chloride (PVC), polyparaphenylene (PPP), polyacrylonitrile (PAN), and polystyrene (PS) are soluble at the rate of 1. at 50% by weight, and preferably from 1 to 20% by weight.
  • PVC polyvinyl chloride
  • PPP polyparaphenylene
  • PAN polyacrylonitrile
  • PS polystyrene
  • the solubility of the polymer in the solvent is indicated by a cross (X).
  • PPP is very resistant to chemical attack and that only dichloromethane can solubilize it.
  • the polymer is polystyrene, and the solvent is 2-butanone.
  • the dissolution of the polymer in the solvent is generally carried out with stirring, for example for a period of time sufficient for the dissolution of the polymer in the solvent to be complete.
  • the concentration of the polymer in the solution can be up to the solubility limit of the polymer in the chosen solvent, and it can be, for example, from 10 g / liter of solvent to 200 g / liter of solvent.
  • silicon particles which are generally in the form of a powder.
  • the silicon particles may be micrometric particles, that is to say particles whose size defined by their largest dimension (ie for example the diameter in the case of spherical particles) is from 1 to 200 microns, preferably from 1 to 45 micrometers.
  • the silicon particles may be nanometric particles, that is to say particles whose size defined by their largest dimension (that is to say for example the diameter in the case of spherical particles) is from 5 to 1000 nanometers, preferably from 5 to 100 nanometers.
  • micrometric or nanometric silicon particles may be commercially available nanometric or micrometric particles.
  • silicon has a native oxide layer and commercial silicon is generally slightly oxidized.
  • the silicon oxide SiO 2 does not have good electrochemical performance and should preferably be avoided.
  • step a) when silicon thus synthesized is used, it is preferable to carry out step a) under a controlled atmosphere, such as an argon atmosphere, for example by mixing the silicon particles in the polymer solution in a box. gloves.
  • a controlled atmosphere such as an argon atmosphere
  • the mixture of the silicon particles with the solution of the polymer without an oxygen atom is generally carried out with stirring, for example by means of a magnetic stirrer, and the mixture is generally homogenized using ultrasound, whereby it is obtained a homogeneous dispersion of silicon particles in the polymer solution.
  • the concentration of the silicon particles in the dispersion can be from 0.1 to 50 g / l.
  • a dispersant can be added to the polymer solution during step a) in order to avoid the agglomeration of the silicon particles during the polymer / silicon mixture before atomization.
  • This dispersant can be, for example, CarboxyMethylCellulose (CMC) or, more generally, an anionic surfactant such as sodium dodecyl sulfate; cationic such as cetyl trimethyl ammonium bromide; or neutral such as polyethylene glycol octylphenyl ether.
  • CMC CarboxyMethylCellulose
  • anionic surfactant such as sodium dodecyl sulfate
  • cationic such as cetyl trimethyl ammonium bromide
  • neutral polyethylene glycol octylphenyl ether
  • the dispersant generally intervenes at a level of 0.1 to 100 mmol / g of material to be dispersed.
  • this dispersion is subjected to an atomization-drying operation which makes it possible to encapsulate the silicon particles by the polymer, the latter then being pyrolyzed.
  • This atomization-drying operation can be carried out in a conventional apparatus, drying atomization current which is commonly used in the pharmaceutical and food industries such as that illustrated in FIG. figure 1 .
  • the dispersion is introduced at the top of an atomizer, atomization tower, passing through a nozzle (see figure 2 ) which atomizes, sprays the dispersion into droplets.
  • the temperature of the nozzle is generally adjusted according to the boiling point (Tb) of the solvent of the dispersion.
  • Tb boiling point
  • the maximum temperature of the nozzle or Tbusemax is preferably about Tb + 30 ° C while the minimum temperature of the nozzle or Tbusemin is preferably about Tb -20 ° C.
  • the nozzle may thus be generally brought to a temperature of 220 ° C., preferably 60 ° C. to 110 ° C.
  • the temperature of the nozzle can be lowered.
  • the droplets thus formed are then dried by a stream of hot gas, for example hot air, which evaporates the solvent, before falling on the inner walls of the apparatus.
  • a stream of hot gas for example hot air, which evaporates the solvent
  • the silicon / polymer composite material generally in the form of a powder, is generally collected with the aid of a cyclone.
  • the gas, such as air, loaded with solvent is generally cooled in a heat exchanger and then condensed in a refrigeration unit, and finally recovered in a tray provided for this purpose.
  • the gas such as air is, for its part, generally re-injected into the atomizer.
  • the atomization-drying makes it possible to obtain a polymer / silicon composite of morphology that is generally spherical or spheroidal and of controlled particle size.
  • the silicon / polymer composite material contains silicon particles trapped in a polymer matrix and is generally in the form of particles.
  • the polymer-coated silicon particles obtained at the end of the atomization-drying operation are spherical or spheroidal and generally have a diameter of 1 micrometer to 20 micrometers in the case of nanometric silica particles. is shown on the figure 5 .
  • the particles usually form a powder.
  • the morphology and controlled particle size mentioned above ensure that at the end of the pyrolysis a strong interface between silicon and carbon is preserved.
  • the silicon / polymer composite material generally consisting of a powder formed by silicon particles coated with the polymer is then, in accordance with the process according to the invention, subjected to a thermal pyrolysis treatment at a temperature generally of 600 ° C. to 1100 ° C. vs.
  • This treatment is generally carried out under a controlled atmosphere, namely a non-oxidizing atmosphere such as an argon atmosphere, or an argon and hydrogen atmosphere to minimize oxidation.
  • a controlled atmosphere namely a non-oxidizing atmosphere such as an argon atmosphere, or an argon and hydrogen atmosphere to minimize oxidation.
  • Pyrolysis can be carried out in an apparatus such as a tube furnace under argon flow.
  • the final Si / C composite material obtained by the process according to the invention is for example figure 5 ) in the form of silicon particles coated with carbon, more exactly by a carbon matrix. These particles generally form clusters or aggregates of Si and C and generally have a nanoscale dimension.
  • the Si / C composite material may for example be in the form of particles generally forming a powder.
  • the composite material thus prepared by the process according to the invention can be used as an electrochemically active material in any electrochemical system.
  • the composite material prepared by the process according to the invention can in particular be used as electrochemically active material of positive or negative electrode in any electrochemical system with non-aqueous electrolyte.
  • This positive or negative electrode comprises, besides the electrochemically active material of positive or negative electrode as defined above, a binder which is generally an organic polymer, optionally one or more additive (s) conductor (s) electronic (s), and a current collector.
  • a binder which is generally an organic polymer, optionally one or more additive (s) conductor (s) electronic (s), and a current collector.
  • the organic polymer may be chosen from polytretrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and the PVDF-HFP copolymer (propylene hexafluoride); and elastomers such as CMC-SBR (carboxymethylcellulose-rubber styrene butadiene).
  • PTFE polytretrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVDF-HFP copolymer propylene hexafluoride
  • elastomers such as CMC-SBR (carboxymethylcellulose-rubber styrene butadiene).
  • the optional electronic conductive additive may be chosen from metal particles such as Ag particles, graphite, carbon black, carbon fibers, carbon nanowires, carbon nanotubes and electronically conductive polymers, and their mixtures.
  • the current collector is generally in the form of a sheet of copper, nickel or aluminum.
  • the electrode generally comprises from 70 to 94% by weight of electrochemically active material, from 1 to 20% by weight, preferably from 1 to 10% by weight of the binder, and optionally from 1 to 15% by weight of the additive (s). (s) electronic driver (s).
  • Such an electrode can be prepared in a conventional manner by forming a suspension, paste or ink with the electrochemically active material, the binder, optionally the conductive additive (s) and a solvent, by depositing, coating or printing this suspension, paste or ink on a current collector, drying the ink, deposited paste or suspension, and calendering, pressing the ink or paste deposited, dried and the current collector.
  • Si / C composite material prepared by the process according to the invention does not require significant mechanical grinding, since a simple mortar grinding which does not affect in any way the properties of the composite are sufficient to break agglomerates that may be present.
  • the ink, paste or suspension can be applied by any suitable method such as coating, coating, gravure, flexography, offset.
  • the electrochemical system may in particular be a rechargeable electrochemical accumulator with non-aqueous electrolyte such as an accumulator or a lithium battery, and more particularly a lithium ion accumulator, which in addition to the positive or negative electrode as defined above, comprising in particular as electrochemically activates the composite material prepared by the process according to the invention, comprises a negative or positive electrode which does not comprise the composite material obtained by the process according to the invention, and a non-aqueous electrolyte.
  • a rechargeable electrochemical accumulator with non-aqueous electrolyte such as an accumulator or a lithium battery
  • a lithium ion accumulator which in addition to the positive or negative electrode as defined above, comprising in particular as electrochemically activates the composite material prepared by the process according to the invention, comprises a negative or positive electrode which does not comprise the composite material obtained by the process according to the invention, and a non-aqueous electrolyte.
  • the negative or positive electrode which does not comprise as an electrochemically active material the composite material obtained by the process according to the invention, comprises an electrochemically active material different from the composite material obtained by the process according to the invention, a binder, optionally one or more additive (s) conductor (s) electronic (s) and a current collector.
  • the electrochemically active material of the negative or positive electrode which does not comprise the composite material obtained by the process according to the invention as an electrochemically active material may be chosen from all the materials known to those skilled in the art.
  • the electrochemically active material of the positive electrode when the composite material obtained by the process according to the invention is the electrochemically active material of the positive electrode, then the electrochemically active material of the negative electrode can be chosen from lithium and any material known to those skilled in the art. in this field of the art.
  • the electrochemically active material of the negative electrode is formed by the material obtained by the process according to the invention
  • the electrochemically active material of the positive electrode can be made of any material known and adaptable by the skilled person.
  • the electrolyte may be solid or liquid.
  • the electrolyte When the electrolyte is liquid, it consists for example of a solution of at least one conductive salt such as a lithium salt in an organic solvent and / or an ionic liquid.
  • the electrolyte When the electrolyte is solid, it comprises a polymeric material and a lithium salt.
  • the lithium salt may be chosen for example from LiAsF 6 , LiClO 4 , LiBF 4 , LiPF 6 , LiBOB, LiODBF, LiB (C 6 H 5 ), LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 (LiTFSI) , LiC (CF 3 SO 2 ) 3 (LiTFSM).
  • the organic solvent is preferably a solvent compatible with the constituents of the electrodes, relatively nonvolatile, aprotic and relatively polar.
  • ethers, esters and mixtures thereof may be mentioned.
  • the ethers are chosen in particular from linear carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC), dipropyl carbonate (DPC), cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate; alkyl esters such as formates, acetates, propionates and butyrates; gamma butyrolactone, triglyme, tetraglyme, lactone, dimethylsulfoxide, dioxolane, sulfolane and mixtures thereof.
  • the solvents are preferably mixtures including EC / DMC, EC / DEC, EC / DPC and EC / DMC.
  • the accumulator may have the shape of a button cell.
  • buttons cell in 316L stainless steel, are described on the figure 3 .
  • a silicon / carbon composite material is prepared by the process according to the invention.
  • Polystyrene (PS) in 2-butanone is dissolved under stirring at concentrations ranging from 200 g / liter of solvent to 10 g / liter of solvent.
  • the preferred solution is 60 g / liter.
  • each of the polystyrene solutions of silicon is added in the form of a nanoparticle powder of size less than 100 nm from Aldrich ®, and homogenized by ultrasound and magnetic stirring. Dispersions of silicon particles in the polystyrene solutions are thus obtained, for example a dispersion of 60 g of PS per liter of solvent and 3 g of Si per liter of solvent.
  • Each of these dispersions is then introduced into a spray-drying device namely a "mini spray dryer B290" apparatus from Buchi ®.
  • Each of the dispersions passes into the nozzle of the spray-drying device with a nozzle temperature of between 60 ° C (Tbusemin) and 110 ° C (Tbusemax).
  • Tbusemin 60 ° C
  • Tbusemax 110 ° C
  • the solvent evaporates and a powder consisting of silicon particles coated with polystyrene or rather of a polymer matrix with inclusions of Si, is recovered in the tank of the atomizing apparatus.
  • the particles of Si / PS composite material obtained after the atomization-drying of a dispersion comprising 3 g of Si per liter of solvent and 60 g of PS per liter of solvent are spherical with a diameter of between 1 micrometer and 20 microns for an initial Si powder diameter of 5 to 100 nm.
  • the size of the composite material particles increases.
  • This powder of silicon particles coated with polystyrene (Si / PS composite) is then pyrolyzed in a tubular furnace at various constant temperatures between 600 ° C. and 1100 ° C., for example at 800 ° C. and 900 ° C. under a controlled atmosphere. argon and hydrogen to minimize oxidation.
  • the Si / C composite powder obtained after pyrolysis at 900 ° C. of the powder of the figure 4 has a nanometric structure.
  • the particles of this powder are silica particles embedded in a carbon matrix.
  • Example 2 The Si / C composite materials prepared in Example 1 were then tested as a positive electrode active material in "coin-button” type lithium-metal batteries ( half-cell test ). These tests are the subject of Examples 2 to 4.
  • the stainless steel case is then closed with a crimper, making it perfectly airtight. To check if the batteries are operational, these are controlled by the measurement of the voltage at the abandonment.
  • the button cell Due to the high reactivity of lithium and its salts with oxygen and water, the button cell is put in a glove box. This is maintained in slight overpressure under anhydrous argon atmosphere. Sensors provide continuous monitoring of oxygen and water concentrations. Typically, these concentrations should remain below the ppm.
  • the Si / C composite materials prepared by the process according to the invention in Example 1, and mounted in the button cells in accordance with the procedure described above undergo cycling, that is to say charges and discharges. at different constant current regimes, for a given number of cycles, to evaluate the practical capacity of the battery.
  • a battery that charges at C / 20 is a battery which is imposed a constant current for 20 hours in order to recover its full capacity C.
  • the current value is equal to the capacity C divided by the number of hours of charging ie in this case 20 hours.
  • the electrode active material comprises an Si / C composite material prepared in accordance with Example 1 above by pyrolysis of an Si / PS composite ( figure 4 ) at a temperature of 900 ° C.
  • a battery comprising the same active electrode material as that of Example 2 is subjected to a test according to a second cycling protocol comprising 35 charge / discharge cycles at C / 2.5. It can be seen that the capacity is around 800 mAh / g with a very small capacity decrease as shown on the figure 7 .
  • an electrode active material comprising an Si / C composite material prepared according to Example 1 above by pyrolysis of an Si / PS composite ( figure 4 ) at a temperature of 900 ° C and those of an electrode active material comprising an Si / C composite material prepared according to Example 1 above by pyrolysis of an Si / PS composite ( figure 4 ) at a temperature of 800 °.
  • the composite material prepared by pyrolysis at 900 ° C. gives better electrochemical performances.
  • the capacity is stable for the C / 10 and C / 5 regimes, unlike the cell whose positive electrode active material comprises a composite material prepared by pyrolysis at 800 ° C. Capacity is slightly less important for low speeds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Combustion & Propulsion (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Claims (15)

  1. Verfahren zur Herstellung eines Silicium/Kohlenstoff-Kompositmaterials, gebildet durch mit Kohlenstoff umhüllte Siliciumpartikel, bei dem man die folgenden sukzessiven Schritte ausführt:
    a) man mischt die Siliciumpartikel mit einer Lösung aus einem Polymer ohne Sauerstoff in einem Lösungsmittel, wodurch man eine Dispersion von Siliciumpartikeln in der Lösung des Polymers erhält;
    b) man unterzieht die in dem Schritt a) erhaltene Dispersion einer Atomisierungs-Trocknungs-Operation, wodurch man ein Silicium/Polymer-Verbundmaterial erhält, gebildet durch von dem Polymer umhüllte Siliziumpartikel ;
    c) man pyrolisiert das in dem Schritt b) erhaltene Material, wodurch man das Silicium/Kohlenstoff-Verbundmaterial erhält, gebildet durch von Kohlenstoff umhüllte Siliciumpartikel.
  2. Verfahren nach Anspruch 1, bei dem das Polymer ausgewählt wird unter dem Polystyrol (PS), dem Polyvinylchlorid (PVC), dem Polyethylen, dem Polyacrylnitril (PAN) und dem Polyparaphenylen (PPP).
  3. Verfahren nach Anspruch 1, bei dem das Lösungsmittel ausgewählt wird unter halogenisierten Alkanen wie zum Beispiel dem Dichlormethan ; den Ketonen wie zum Beispiel dem Aceton und dem 2-Butanon ; dem Tetrahydrofuran (THF) ; dem N-Methylpyrrolidon (NMP) ; dem Acetonitril ; dem Dimethylformamid (DMF) ; dem Dimethylsulfoxid (DMSO) ; und ihren Mischungen.
  4. Verfahren nach Anspruch 1, bei dem das Polymer das Polystyrol ist, und das Lösungsmittel das 2-Butanon ist.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Konzentration des Polymers in der Lösung von 10 g/Liter des Lösungsmittels bis 200 g/Liter des Lösungsmittels beträgt.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Siliciumpartikel mikrometrische Partikel sind.
  7. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Siliciumpartikel nanometrische Partikel sind.
  8. Verfahren nach Anspruch 7, bei dem die Siliciumpartikel durch Reduktion von SiCl4 synthetisierten Silicium Partikeln, unter einer kontrollierten Atmosphäre, vorzugsweise unter Argon, sind.
  9. Verfahren nach Anspruch 8, bei dem der Schritt a) realisiert wird unter einer kontrollierten Atmosphäre, vorzugsweise unter Argon.
  10. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Konzentration der Siliciumpartikel in der Dispersion 0,1 bis 50 g/l beträgt.
  11. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die von Polymer umhüllten Siliciumpartikel sphärisch sind und zum Beispiel einen Durchmesser von 1 Mikrometer bis 20 Mikrometer haben.
  12. Verfahren nach einem der vorhergehenden Ansprüche, bei dem man außerdem in Schritt a) ein Dispersionsmittel beigibt.
  13. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Dispersion in Schritt b) durch eine auf eine Temperatur von 20°C bis 220 °C, vorzugsweise von 60°C bis 110°C gebrachte Düse zerstäubt wird .
  14. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Schritt c) bei einer Temperatur von 600 °C bis 1100 °C, vorzugsweise von 800 °C bis 900 °C ausgeführt wird.
  15. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Schritt c) unter einer kontrollierten Atmosphäre realisiert wird, zum Beispiel einer Argon- oder einer Argonund Wasserstoffatmosphäre.
EP09782886.7A 2008-09-12 2009-09-10 Verfahren zur herstellung eines silicium/kohlenstoff-verbundwerkstoffs Active EP2323960B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0856158A FR2936102B1 (fr) 2008-09-12 2008-09-12 Procede de preparation d'un materiau composite silicium/ carbone, materiau ainsi prepare et electrode notamment electrode negative, comprenant ce materiau.
PCT/EP2009/061772 WO2010029135A2 (fr) 2008-09-12 2009-09-10 Procédé de préparation d'un matériau composite silicium/carbone, matériau ainsi préparé et électrode notamment electrode negative, comprenant ce matériau

Publications (2)

Publication Number Publication Date
EP2323960A2 EP2323960A2 (de) 2011-05-25
EP2323960B1 true EP2323960B1 (de) 2016-12-14

Family

ID=40580860

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09782886.7A Active EP2323960B1 (de) 2008-09-12 2009-09-10 Verfahren zur herstellung eines silicium/kohlenstoff-verbundwerkstoffs

Country Status (6)

Country Link
US (1) US20110165468A1 (de)
EP (1) EP2323960B1 (de)
JP (1) JP5651593B2 (de)
CN (1) CN102149654B (de)
FR (1) FR2936102B1 (de)
WO (1) WO2010029135A2 (de)

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101378125B1 (ko) * 2010-04-19 2014-03-25 주식회사 엘지화학 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
CN101931076B (zh) * 2010-07-30 2014-01-29 中国科学院化学研究所 一种硅碳复合颗粒的制备方法及其作为锂离子电池负极材料的应用
US10673062B1 (en) * 2019-11-08 2020-06-02 Enevate Corporation Method and system for thermal gradient during electrode pyrolysis
WO2013031993A1 (ja) * 2011-08-31 2013-03-07 国立大学法人東北大学 Ｓｉ／Ｃ複合材料及びその製造方法並びに電極
CA2752844A1 (en) * 2011-09-19 2013-03-19 Hydro-Quebec Method for preparing a particulate of si or siox-based anode material, and material thus obtained
FR2980191B1 (fr) * 2011-09-20 2014-10-24 Commissariat Energie Atomique Procede de fabrication d'un materiau composite silicium/carbone et utilisation d'un tel materiau
FR2981643B1 (fr) * 2011-10-25 2013-12-27 Commissariat Energie Atomique Procede de preparation d'un materiau composite silicium/carbone, materiau ainsi prepare, et electrode notamment electrode negative, comprenant ce materiau.
CN103137952A (zh) * 2011-11-22 2013-06-05 宁波杉杉新材料科技有限公司 一种锂离子电池硅基复合负极材料及其制备方法
CN102558450B (zh) * 2011-12-21 2013-09-25 北京工商大学 一种提高聚丙烯熔体强度的方法
JP5602262B2 (ja) * 2013-01-29 2014-10-08 昭和電工株式会社 複合電極材
FR3004856B1 (fr) 2013-04-23 2016-05-06 Commissariat Energie Atomique Dispositif de gestion d'un accumulateur
KR101458309B1 (ko) * 2013-05-14 2014-11-04 오씨아이 주식회사 부피 변화를 완화할 수 있는 Si-블록 공중합체 코어-쉘 나노 입자 및 이를 이용한 리튬 이차전지용 음극활물질
JP2015022964A (ja) * 2013-07-22 2015-02-02 株式会社デンソー リチウムイオン二次電池用負極材料，その製造方法及びリチウムイオン二次電池
JP6132173B2 (ja) * 2014-01-31 2017-05-24 株式会社豊田自動織機 非水系二次電池用負極及び非水系二次電池、負極活物質及びその製造方法、ナノシリコンと炭素層とカチオン性ポリマー層とを具備する複合体、ナノシリコンと炭素層よりなる複合体の製造方法
EP2919298B1 (de) * 2014-03-12 2017-08-23 Belenos Clean Power Holding AG Si/C-Kompositanoden für Lithium-Ionen-Batterien mit anhaltender hoher Kapazität pro Flächeneinheit
KR101572364B1 (ko) * 2014-03-19 2015-11-26 오씨아이 주식회사 탄소-실리콘 복합체, 이를 이용한 리튬 이차전지용 음극 및 리튬 이차전지
FR3018955B1 (fr) * 2014-03-24 2016-05-06 Commissariat Energie Atomique Procede de fabrication d'une electrode, electrode ainsi fabriquee et systeme electrochimique la comprenant.
KR101567203B1 (ko) 2014-04-09 2015-11-09 (주)오렌지파워 이차 전지용 음극 활물질 및 이의 방법
KR101807348B1 (ko) * 2014-05-09 2017-12-08 주식회사 엘지화학 실리콘-탄소 복합체, 이의 제조방법 및 이를 포함하는 음극 활물질
KR101615439B1 (ko) * 2014-07-17 2016-05-13 오씨아이 주식회사 탄소-실리콘 복합체의 제조방법
EP3180289A1 (de) * 2014-08-12 2017-06-21 The Regents of the University of California Lithiumsulfid-graphenoxid-verbundstoff für li/s-zellen
KR20160049980A (ko) * 2014-10-28 2016-05-10 레르 리키드 쏘시에떼 아노님 뿌르 레뜌드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 규소/탄소 복합재, 규소 합금/탄소 복합재, 및 그의 제조 방법
KR101826391B1 (ko) * 2015-03-31 2018-02-06 주식회사 엘지화학 다공성 실리콘-실리콘옥사이드-탄소 복합체, 및 이의 제조방법
US10427982B2 (en) 2015-09-17 2019-10-01 Korea Institute Of Energy Research Method of carbon coating on nanoparticle and carbon coated nanoparticle produced by the same
KR101678187B1 (ko) * 2015-09-17 2016-11-22 한국에너지기술연구원 나노입자의 탄소 코팅 방법 및 이에 의해 제조된 탄소 코팅된 나노입자
DE102016203349A1 (de) 2016-03-01 2017-09-07 Wacker Chemie Ag Herstellung von Si/C-Kompositpartikeln
KR102171131B1 (ko) 2016-08-11 2020-10-29 와커 헤미 아게 Ｓｉ/ｃ 복합 입자의 제조
WO2018146865A1 (ja) * 2017-02-09 2018-08-16 株式会社村田製作所 二次電池、電池パック、電動車両、電動工具および電子機器
WO2018145747A1 (de) * 2017-02-09 2018-08-16 Wacker Chemie Ag Redispergierbare partikel basierend auf siliciumpartikeln und polymeren
GB2563455B (en) 2017-06-16 2019-06-19 Nexeon Ltd Particulate electroactive materials for use in metal-ion batteries
GB201803983D0 (en) 2017-09-13 2018-04-25 Unifrax I Llc Materials
US11258058B2 (en) * 2019-11-08 2022-02-22 Enevate Corporation Silicon carbon composite powder active material
WO2019131519A1 (ja) * 2017-12-27 2019-07-04 東ソー株式会社 リチウム二次電池用複合活物質およびその製造方法
WO2019150725A1 (ja) * 2018-02-05 2019-08-08 株式会社豊田自動織機 炭素被覆シリコン材料
CN108794038B (zh) * 2018-06-06 2021-08-03 苏州宏久航空防热材料科技有限公司 一种基于原位聚合的低成本碳纤维增强碳基复合材料的制备方法
CN109585785A (zh) * 2018-11-22 2019-04-05 江苏科技大学 一种基于废塑料制备Si/CNF/C复合材料及锂电子电池负极材料的方法
WO2021018598A1 (en) * 2019-07-26 2021-02-04 Enwires Composite material and method for preparing same
CN116364877A (zh) 2019-07-29 2023-06-30 宁德时代新能源科技股份有限公司 负极活性材料及二次电池
CN112310356B (zh) 2019-07-29 2022-06-07 宁德时代新能源科技股份有限公司 负极活性材料及二次电池
US20230101574A1 (en) * 2020-03-18 2023-03-30 Wacker Chemie Ag Method for producing carbon-coated silicon particles
CN113666354B (zh) * 2020-05-13 2023-04-04 北京小米移动软件有限公司 一种硅碳复合材料的制备方法、硅负极极片及电池
CN112563502A (zh) * 2020-12-07 2021-03-26 广东凯金新能源科技股份有限公司 一种高首效多元包覆硅基复合材料、其制备方法及其应用
CN113104852B (zh) * 2021-03-16 2022-04-05 北京科技大学 一种锂离子电池硅碳负极材料的制备方法
KR102517722B1 (ko) * 2021-05-31 2023-04-04 주식회사 비이아이랩 기상 전기 환원법을 이용한 실리콘의 제조방법
CN114142005B (zh) * 2021-11-09 2023-03-31 广东凯金新能源科技股份有限公司 一种长循环、低膨胀内孔结构硅碳复合材料、其制备方法及其应用
TWI805123B (zh) * 2021-12-10 2023-06-11 芯量科技股份有限公司 矽碳複合負極材料及其製備方法與應用
CN114920242B (zh) * 2022-05-23 2023-05-05 格龙新材料科技(常州)有限公司 一种高容量石墨复合材料的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732180A (en) * 1970-11-18 1973-05-08 Eastman Kodak Co Photoconductive composition and method
JP3897709B2 (ja) * 2002-02-07 2007-03-28 日立マクセル株式会社 電極材料およびその製造方法、並びに非水二次電池用負極および非水二次電池
JP4188156B2 (ja) * 2003-06-24 2008-11-26 株式会社東芝 粒子形成方法及び粒子形成装置
CN1913200B (zh) * 2006-08-22 2010-05-26 深圳市贝特瑞电子材料有限公司 锂离子电池硅碳复合负极材料及其制备方法
WO2009068884A1 (en) * 2007-11-28 2009-06-04 National University Of Singapore Multilayer heterostructures for application in oleds and photovoltaic devices

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2323960A2 (de) 2011-05-25
CN102149654B (zh) 2014-07-30
FR2936102B1 (fr) 2010-10-29
WO2010029135A3 (fr) 2010-09-16
JP2012501951A (ja) 2012-01-26
CN102149654A (zh) 2011-08-10
JP5651593B2 (ja) 2015-01-14
US20110165468A1 (en) 2011-07-07
WO2010029135A2 (fr) 2010-03-18
FR2936102A1 (fr) 2010-03-19

Similar Documents

Publication Publication Date Title
EP2323960B1 (de) Verfahren zur herstellung eines silicium/kohlenstoff-verbundwerkstoffs
EP2661779B1 (de) Silicium-/kohlenstoffverbundmaterial, verfahren zu seiner synthese und verwendung eines derartigen materials
EP1722429B1 (de) Nanoverbundstoff-Material als Anode einer Lithium-Sekundärbatterie
EP2396841B1 (de) Verfahren zur herstellung einer mischung aus einer elektrodenaktiven pulververbindung und elektrisch leitende pulververbindung, daraus resultierende mischung sowie elektrode, zelle und batterie dafür
FR2935546A1 (fr) Materiau composite d'electrode, electrode de batterie constituee dudit materiau et batterie au lithium comprenant une telle electrode.
EP3298644B1 (de) Positivelektrode für einen elektrochemischen lithiumgenerator
TW201437143A (zh) 做爲鋰離子電池陽極材料之Ｓｉ／Ｃ複合物
WO2010106292A1 (fr) Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium
WO2014060532A1 (fr) Materiau composite comprenant des nano-objets notamment des nano-objets de carbone, son procede de preparation, et encre et electrode comprenant ce materiau
WO2019158891A1 (fr) Formulation de matière active pour accumulateur li-s et procédé de préparation
EP3740984A1 (de) Formulierung in form einer fest-flüssig-dispersion zur herstellung einer kathode für eine li/s-batterie und verfahren zur herstellung dieser formulierung
FR3071361B1 (fr) Procede de fabrication d'une electrode pour accumulateur lithium-soufre utilisant du li2s comme materiau actif
EP3052441B1 (de) Elektrode für eine stromspeicherbatterie mit einem graphit-/silicium-/kohlefaserverbundstoff
WO2022251968A1 (fr) Matériaux d'enrobage à base d'hydrocarbures aliphatiques insaturés et leurs utilisations dans des applications électrochimiques
EP3483953A2 (de) Spezielle zusammensetzung für die herstellung von elektroden, die für eine lithiumbatterie bestimmt sind
EP3887436A1 (de) Leitender polymerelektrolyt für batterien
EP3327832B1 (de) Verfahren zur herstellung einer positiven elektrode für eine lithium-schwefel-batterie
FR3071362B1 (fr) Procede de fabrication d'une electrode pour accumulateur lithium-soufre a surface active importante
WO2017216501A1 (fr) Procede de fabrication d'une structure faisant office d'electrode positive et de collecteur de courant pour accumulateur electrochimique lithium-soufre

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110316

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ALIAS, MELANIE

Inventor name: LE CRAS, FREDERIC

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140116

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602009043100

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C04B0035628000

Ipc: H01M0004380000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 10/052 20100101ALI20160622BHEP

Ipc: H01M 4/133 20100101ALI20160622BHEP

Ipc: H01M 4/587 20100101ALI20160622BHEP

Ipc: H01M 4/134 20100101ALI20160622BHEP

Ipc: H01M 4/36 20060101ALI20160622BHEP

Ipc: H01M 4/38 20060101AFI20160622BHEP

Ipc: C04B 35/628 20060101ALI20160622BHEP

INTG Intention to grant announced

Effective date: 20160713

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 854316

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009043100

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170314

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 854316

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170414

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170314

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170414

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009043100

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20170915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170910

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170910

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20090910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240919

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240917

Year of fee payment: 16